Bio‐Inspired Macromolecular Ordering of Elastomers for Enhanced Contact Electrification and Triboelectric Energy Harvesting

Abstract Triboelectrification of polymers enables mechanical energy harvesting in triboelectric generators, droplet generators, and ferroelectrets. Herein, triboelectric polymers, inspired by the ordering in spider‐silk, with strongly enhanced contact electrification are presented. The ordering in polyether block amide (PEBA) is induced by the addition of inorganic goethite (α‐FeOOH) nanowires that form H‐bonds with the elastomeric matrix. The addition of as little as 0.1 vol% of α‐FeOOH into PEBA increases the surface charge by more than order of magnitude (from 0.069 to 0.93 nC cm^–2). The H‐bonds between α‐FeOOH and PEBA promote the formation of inclusions with higher degree of macromolecular ordering, analogous to the structure of spider silk. The formation of these inclusions is proven via nanoindentation hardness measurements and correlated with H‐bond‐induced chemical changes by Fourier transform infrared spectroscopy and direct scanning calorimetry. Theoretical studies reveal that the irregularity in hardness provides stress accumulation on the polymer surface during contact‐separation. Subsequent molecular dynamic studies demonstrate that stress accumulation promotes the mass‐transfer mechanism of contact electrification. The proposed macromolecular structure design provides a new paradigm for developing materials for applications in mechanical energy harvesting.